Process for preparing p-nitroaromatic amides and products thereof

Abstract

A process for preparing p-nitroaromatic amides is provided which comprises contacting an amide and nitrobenzene in the presence of a suitable solvent system, and reacting the amide and nitrobenzene in the presence of a suitable base and a controlled amount of protic material at a suitable temperature in a confined reaction zone. The p-nitroaromatic amides of the invention can be reduced to p-aminoaromatic amides. In one embodiment, the p-aminoaromatic amide is further reacted with ammonia under conditions which produce the corresponding p-aminoaromatic amine and the amide starting material which can be recycled or with water in the presence of a suitable basic or acidic catalyst under conditions which produce the corresponding p-aminoaromatic amine and the acid or salt thereof corresponding to the amide starting material. In another embodiment, the p-aminoaromatic amine is reductively alkylated to produce alkylated p-aminoaromatic amine. The p-nitroaromatic amide can be reacted with ammonia under conditions which produce the corresponding p-nitroaromatic amine and the amide starting material which can be recycled or with water in the presence of a suitable basic or acidic catalyst under conditions which produce the corresponding p-nitroaromatic amine and the acid or salt thereof corresponding to the amide starting material. In one embodiment, the p-nitroaromatic amine is reduced to produce p-aminoaromatic amine. In another embodiment, the p-aminoaromatic amine is reductively alkylated to produce alkylated p-aminoaromatic amine. In another embodiment, the p-nitroaromatic amine is reductively alkylated to produce p-aminoaromatic amine.

What is claimed is: N-(4-nitroaromatic) 
     
       1. A process for preparing p-nitroaromatic amides comprising: (a) contacting an amide and nitrobenzene in the presence of a suitable solvent system, and   (b) reacting the amide and nitrobenzene in the presence of a suitable base and a controlled amount of protic material at a suitable temperature in a confined reaction zone.   
     
     
       2. The process of claim 1 wherein said amide is selected from the group consisting of aromatic amides, aliphatic amides, substituted aromatic amide derivatives, substituted aliphatic amide derivatives and diamides having the formula: ##STR4## wherein R 1  and R 2  are independently selected from the group consisting of aromatic groups, aliphatic groups and a direct bond, and A is selected from the group consisting of ##STR5## --SO 2  --, --O, --S-- and a direct bond. 
     
     
       3. The process of claim 2 wherein said aliphatic amides and said substituted aliphatic amide derivatives are represented by the formula: ##STR6## wherein n is 0 or 1, R 3  is selected from the group consisting of alkyl, aryl alkyl, alkenyl, arylalkenyl, cycloalkyl and cycloalkenyl groups and X is selected from the group consisting of hydrogen, --NO 2 , NH 2 , aryl groups, alkoxy groups, sulfonate groups, --SO 3  H, --OH, --COH, --COOH, and alkyl, aryl, arylalkyl or alkylaryl groups containing at least one --NH 2  group. 
     
     
       4. The process of claim 3 wherein said aliphatic amides and said substituted aliphatic amide derivatives are selected from the group consisting of isobutyramide, urea, acetamide and propyl amide. 
     
     
       5. The process of claim 2 wherein the substituent of said substituted aromatic amide derivatives is selected from the group consisting of halides, --NO 2 , --NH 2 , alkyl groups, alkoxy groups, sulfonate groups, --SO 3  H, --OH, --OH, --COOH and alkyl, aryl, arylalkyl or alkylaryl groups containing at least one --NH 2  group, wherein halides are selected from the group consisting of chloride, bromide and fluoride. 
     
     
       6. The process of claim 5 wherein said aromatic amides and said substituted aromatic amide derivatives are selected from the group consisting of benzamide, 4-methylbenzamide, 4-methoxybenzamide, 4-chlorobenzamide, 2-methylbenzamide, 4-nitrobenzamide, and 4-aminobenzamide. 
     
     
       7. The process of claim 2 wherein said diamides are selected from the group consisting of adipamide, oxalic amide, terephthalic diamide, and 4,4'-biphenyldicarboxamide. 
     
     
       8. The process of claim 1 wherein said suitable solvent system includes a solvent selected from the group consisting of nitrobenzene, dimethylsulfoxide, dimethylformamide, N-methyl-2-pyrrolidone, pyridine, N-methylaniline, chlorobenzene, tetrahydrofuran, 1,4-dioxane, tetraalkyl ammonium hydroxide or amides having a melting point below the reaction temperature and mixtures thereof. 
     
     
       9. The process of claim 8 wherein said suitable solvent system includes a protic solvent. 
     
     
       10. The process of claim 1 wherein the molar ratio of said protic material to said suitable base is less than about 5:1 and the ratio of equivalents of said suitable base to equivalents of said amide is about 1:1 to about 10:1. 
     
     
       11. The process of claim I wherein said suitable temperature is from about 5° C. to about 150° C. 
     
     
       12. The process of claim i wherein said suitable base is selected from the group consisting of organic and inorganic bases. 
     
     
       13. The process of claim 12 wherein said organic and inorganic bases are selected from the group consisting of alkali metals, alkali metal hydrides, alkali metal hydroxides, alkali metal alkoxides, phase transfer catalyst in conjunction with a base source, amines, crown ethers in conjunction with a base source, alkyl magnesium halides, and mixtures thereof. 
     
     
       14. The process of claim 1 wherein said base is selected from the group consisting of an aryl ammonium, alkyl ammonium, aryl/alkyl ammonium and alkyl diammonium salt in conjunction with a base source. 
     
     
       15. The process of claim 1 wherein said solvent is nitrobenzene and said base is a tetraalkyl ammonium hydroxide. 
     
     
       16. The process of claim 1 wherein said solvent and said base is a tetraalkyl ammonium hydroxide and said temperature is above the melting point of said tetraalkyl ammonium hydroxide. 
     
     
       17. The process of claim 1 wherein said amide and nitrobenzene are reacted under aerobic conditions. 
     
     
       18. The process of claim 1 wherein said amide and nitrobenzene are reacted under anaerobic conditions. 
     
     
       19. The process of claim 1 wherein a desiccant is present during Step (b) to control the amount of protic material present during the reaction of amide and nitrobenzene. 
     
     
       20. The process of claim 1 wherein the amount of protic material is Step (b) is controlled by the continuous distillation of said protic material. 
     
     
       21. A process for preparing N-(4-aminoaromatic) amides comprising: (a) contacting an amide and nitrobenzene in the presence of a suitable solvent system,   (b) reacting the amide and nitrobenzene in the presence of a suitable base and a controlled amount of protic material at a suitable temperature in a confined reaction zone, and   (c) reducing the reaction product of (b) under conditions which produce N-(4-aminoaromatic) amides.   
     
     
       22. The process of claim 21 wherein said amide is selected from the group consisting of aromatic amides, aliphatic amides, substituted aromatic amide derivatives, substituted aliphatic amide derivatives and diamides having the formula: ##STR7## wherein R 1  and R 2  are independently selected from the group consisting of aromatic groups, aliphatic groups and a direct bond, and A is selected from the group consisting of ##STR8## --SO 2  --, --O--, --S-- and a direct bond. 
     
     
       23. The process of claim 22 wherein said aliphatic amides and said substituted aliphatic amide derivatives are represented by the formula: ##STR9## wherein n is 0 or 1, R 3  is selected from the group consisting of alkyl, arylalkyl, alkenyl, arylalkenyl, cycloalkyl and cycloalkenyl groups and X is selected from the group consisting of hydrogen, --NO 2 , --NH 2 , aryl groups, alkoxy groups, sulfonate groups, --SO 3  H, --OH, --COH, --COOH, and alkyl, aryl, arylalkyl or alkylaryl groups containing at least one --NH 2  group. 
     
     
       24. The process of claim 23 wherein said aliphatic amides and said substituted aliphatic amide derivatives are selected from the group consisting of isobutyramide, urea, acetamide and propyl amide. 
     
     
       25. The process of claim 22 wherein the substituent of said substituted aromatic amide derivatives is selected from the group consisting of halides, --NO 2 , --NH 2 , alkyl groups, alkoxy groups, sulfonate groups, --SO 3  H, --OH, --COH, --COOH and alkyl, aryl, arylalkyl or alkyl aryl groups containing at least one --NH 2  group, wherein halides are selected from the group consisting of chloride, bromide and fluoride. 
     
     
       26. The process of claim 25 wherein said aromatic amides and said substituted aromatic amide derivatives are selected from the group consisting of benzamide, 4-methylbenzamide, 4-methoxybenzamide, 4-chlorobenzamide, 2-methylbenzamide, 4-nitrobenzamide, and 4-aminobenzamide. 
     
     
       27. The process of claim 22 wherein said diamides are selected from the group consisting of adipamide, oxalic amide, terephthalic diamide, and 4,4'-biphenyldicarboxamide. 
     
     
       28. The process of claim 21 wherein said suitable solvent system includes a solvent selected from the group consisting of nitrobenzene, dimethylsulfoxide, dimethylformamide, N-methyl-2-pyrrolidone, pyridine, N-methylaniline, chlorobenzene, tetrahydrofuran, 1,4-dioxane, tetraalkyl ammonium hydroxide or amides having a melting point below the reaction temperature and mixtures thereof. 
     
     
       29. The process of claim 28 wherein said suitable solvent system includes a protic solvent. 
     
     
       30. The process of claim 21 wherein the molar ratio of said protic material to said suitable base is less than about 5:1 and the ratio of equivalents of said suitable base to equivalents of said amide is about 1:1 to about 10:1. 
     
     
       31. The process of claim 21 wherein said suitable temperature is from about 5° C. to about 150° C. 
     
     
       32. The process of claim 21 wherein said suitable base is selected from the group consisting of organic and inorganic bases. 
     
     
       33. The process of claim 32 wherein said organic and inorganic bases are selected from the group consisting of alkali metals, alkali metal hydrides, alkali metal hydroxides, alkali metal alkoxides, phase transfer catalyst in conjunction with a base source, amines, crown ethers in conjunction with a base source, alkyl magnesium halides, and mixtures thereof. 
     
     
       34. The process of claim 21 wherein said base is selected from the group consisting of an aryl ammonium, alkyl ammonium, aryl/alkyl ammonium and alkyl diammonium salt in conjunction with a base source. 
     
     
       35. The process of claim 21 wherein said solvent is nitrobenzene and said base is a tetraalkyl ammonium hydroxide. 
     
     
       36. The process of claim 21 wherein said solvent and said base is a tetraalkyl ammonium hydroxide and said temperature is above the melting point of said tetraalkyl ammonium hydroxide. 
     
     
       37. The process of claim 21 wherein said amide and nitrobenzene are reacted under aerobic conditions. 
     
     
       38. The process of claim 21 wherein said amide and nitrobenzene are reacted under anaerobic conditions. 
     
     
       39. The process of claim 21 wherein a desiccant is present during Step (b) to control the amount of protic material present during the reaction of amide and nitrobenzene. 
     
     
       40. The process of claim 21 wherein the amount of protic material is Step (b) is controlled by the continuous distillation of said protic material. 
     
     
       41. The process of claim 21 further comprising: (d) reacting the N-(4-aminoaromatic) amide with ammonia under conditions which produce the corresponding N-(4-aminoaromatic) amine and amide.   
     
     
       42. The process of claim 41 further comprising: (e) reductively alkylating the N-(4-aminoaromatic) amine to produce alkylated N-(4-aminoaromatic) amine.   
     
     
       43. The process of claim 42 wherein said N-(4-aminoaromatic) amine is reductively alkylated utilizing a compound selected from the group consisting of ketones and aldehydes. 
     
     
       44. The process of claim 43 wherein said ketone is selected from the group consisting of acetone, methylisobutylketone, methylisoamylketone and 2-octanone. 
     
     
       45. The process of claim 21 further comprising: (d) reacting the N-(4-aminoaromatic) amide with water in the presence of a suitable basic or acidic catalyst under conditions which produce the corresponding N-(4-aminoaromatic) amine and the acid or salt thereof corresponding to said amide of (a).   
     
     
       46. The process of claim 45 further comprising: (e) reductively alkylating the N-(4-aminoaromatic) amine to produce alkylated N-(4-aminoaromatic) amine.   
     
     
       47. The process of claim 46 wherein said N-(4-aminoaromatic) amine is reductively alkylated utilizing a compound selected from the group consisting of ketones and aldehydes. 
     
     
       48. The process of claim 47 wherein said ketone is selected from the group consisting of acetone, methylisobutylketone, methylisoamylketone and 2-octanone. 
     
     
       49. A process for preparing N-(4-nitroaromatic) amine comprising: (a) contacting an amide and nitrobenzene in the presence of a suitable solvent system,   (b) reacting the amide and nitrobenzene in the presence of a suitable base and a controlled amount of protic material at a suitable temperature in a confined reaction zone, and   (c) reacting the reaction product of (b) with (i) ammonia or (ii) water in the presence of a suitable basic or acidic catalyst under conditions which produce the corresponding N-(4-nitroaromatic) amine and amide or the corresponding acid or salt thereof.   
     
     
       50. The process of claim 49 wherein said amide is selected from the group consisting of aromatic amides, aliphatic amides, substituted aromatic amide derivatives, substituted aliphatic amide derivatives and diamides having the formula: ##STR10## wherein R 1  and R 2  are independently selected from the group consisting of aromatic groups, aliphatic groups and a direct bond, and A is selected from the group consisting of ##STR11## --SO 2  --, --O--, --S-- and a direct bond. 
     
     
       51. The process of claim 50 wherein said aliphatic amides and said substituted aliphatic amide derivatives are represented by the formula: ##STR12## wherein n is 0 or 1, R 3  is selected from the group consisting of alkyl, arylalkyl, alkenyl, arylalkenyl, cycloalkyl and cycloalkenyl groups and X is selected from the group consisting of hydrogen, --NO 2 , --NH 2 , aryl groups, alkoxy groups, sulfonate groups, --SO 3  H, --OH, --COH, --COOH, and alkyl, aryl, arylalkyl or alkylaryl groups containing at least one --NH 2  group. 
     
     
       52. The process of claim 51 wherein said aliphatic amides and said substituted aliphatic amide derivatives are selected from the group consisting of isobutyramide, urea, acetamide and propylamide. 
     
     
       53. The process of claim 50 wherein the substituent of said substituted aromatic amide derivatives is selected from the group consisting of halides, --NO 2 , --NH 2 , alkyl groups, alkoxy groups, sulfonate groups, --SO3H, --OH, --COH, --COOH and alkyl, aryl, arylalkyl or alkylaryl groups containing at least one --NH 2  group, wherein halides are selected from the group consisting of chloride, bromide and fluoride. 
     
     
       54. The process of claim 53 wherein said aromatic amides and said substituted aromatic amide derivatives are selected from the group consisting of benzamide, 4-methylbenzamide, 4-methoxybenzamide, 4-chlorobenzamide, 2-methylbenzamide, 4-nitrobenzamide, and 4-aminobenzamide. 
     
     
       55. The process of claim 50 wherein said diamides are selected from the group consisting of adipamide, oxalic amide, terephthalic diamide, and 4,4'-biphenyldicarboxamide. 
     
     
       56. The process of claim 49 wherein said suitable solvent system includes a solvent selected from the group consisting of nitrobenzene, dimethylsulfoxide, dimethylformamide, N-methyl-2-pyrrolidone, pyridine, N-methylaniline, chlorobenzene, tetrahydrofuran, 1,4-dioxane, tetraalkyl ammonium hydroxide or amides having a melting point below the reaction temperature and mixtures thereof. 
     
     
       57. The process of claim 56 wherein said suitable solvent system includes a protic solvent. 
     
     
       58. The process of claim 49 wherein the molar ratio of said protic material to said suitable base is less than about 5:1 and the ratio of equivalents of said suitable base to equivalents of said amide is about 1:1 to about 10:1. 
     
     
       59. The process of claim 49 wherein said suitable temperature is from about 5° C. to about 150° C. 
     
     
       60. The process of claim 49 wherein said suitable base is selected from the group consisting of organic and inorganic bases. 
     
     
       61. The process of claim 60 wherein said organic and inorganic bases are selected from the group consisting of alkali metals, alkali metal hydrides, alkali metal hydroxides, alkali metal alkoxides, phase transfer catalyst in conjunction with a base source, amines, crown ethers in conjunction with a base source, alkyl magnesium halides, and mixtures thereof. 
     
     
       62. The process of claim 49 wherein said base is selected from the group consisting of an aryl ammonium, alkyl ammonium, aryl/alkyl ammonium and alkyl diammonium salt in conjunction with a base source. 
     
     
       63. The process of claim 49 wherein said solvent is nitrobenzene and said base is a tetraalkyl ammonium hydroxide. 
     
     
       64. The process of claim 49 wherein said solvent and said base is a tetraalkyl ammonium hydroxide and said temperature is above the melting point of said tetraalkyl ammonium hydroxide. 
     
     
       65. The process of claim 49 wherein said amide and nitrobenzene are reacted under aerobic conditions. 
     
     
       66. The process of claim 49 wherein said amide and nitrobenzene are reacted under anaerobic conditions. 
     
     
       67. The process of claim 49 wherein a desiccant is present during Step (b) to control the amount of protic material present during the reaction of amide and nitrobenzene. 
     
     
       68. The process of claim 49 wherein the amount of protic material is Step (b) is controlled by the continuous distillation of said protic material. 
     
     
       69. The process of claim 49 further comprising: (d) reducing the N-(4nitroaromatic) amine under conditions which produce the corresponding N-(4-aminoaromatic amine.   
     
     
       70. The process of claim 69 further comprising: (e) reductively alkylating the N-(4-aminoaromatic) amine to produce alkylated N-(4-aminoaromatic) amine.   
     
     
       71. The process of claim 70 wherein said N-(4-aminoaromatic) amine is reductively alkylated utilizing a compound selected from the group consisting of ketones and aldehydes. 
     
     
       72. The process of claim 71 wherein said ketone is selected from the group consisting of acetone, methylisobutylketone, methylisoamylketone and 2 -octanone. 
     
     
       73. The process of claim 49 further comprising: (d) reductively alkylating the N-(4-nitroaromatic) amine to produce alkylated N-(4-aminoaromatic) amine.   
     
     
       74. The process of claim 73 wherein said N-(4nitroaromatic) amine is reductively alkylated utilizing a compound selected from the group consisting of ketones and aldehydes. 
     
     
       75. The process of claim 74 wherein said ketone is selected from the group consisting of acetone, methylisobutylketone, methylisoamylketone and 2-octanone. 
     
     
       76. The process of claim 49 comprising: (a) contacting an amide and nitrobenzene in the presence of a suitable solvent system;   (b) reacting the amide and nitrobenzene in the presence of a suitable base and a controlled amount of protic material at a suitable temperature in a confined reaction zone, and   (c) reacting the reaction product of (b) with ammonia under conditions which produce the corresponding N-(4nitroaromatic) amine and amide.   
     
     
       77. The process of claim 49 comprising: (a) contacting an amide and nitrobenzene in the presence of a suitable solvent system;   (b) reacting the amide and nitrobenzene in the presence of a suitable base and a controlled amount of protic material at a suitable temperature in a confined reaction zone, and   (c) reacting the reaction product of (b) with water in the presence of a suitable basic or acidic catalyst under conditions which produce the corresponding N-(4-nitroaromatic) amine and the acid or salt thereof corresponding to said amide of (a).